Metallization of insulating substrates

ABSTRACT

THERE ARE PROVIDED COMPOSITIONS TO RENDER INSULTING SUBSTRATES CATALYTIC TO ELECTROLESS METAL DEPOSITION COMPRISING MATERIALS, E.G., SOLID AGENTS, HAVING DEPOSITED THEREON A CATIONIC WETTING AGENT IN COMBINATION WITH AN ELEMENTAL FORM OF A METAL FROM GROUPS I-B AND VIII OF THE PERIODIC TABLE OF ELEMENTS, INCLUDING MIXTURES OF SUCH METALS.

Aug. 17, 197 F. w. SCHNEBLE. JR. ETAIL. ,33

METALLIZATION OF INSULATING SUBSTRATES Filed Jan. 5. 1967 15 Sheets-Sheet 1 INVENTORS mzozmcx w SCHNEBLE,JR EDWARD J. LEECH JOSEPH POLICHETYE BY MORGAN, FINNEGAN, DURHAM & PINE ATTORNEYS u W 1% F. W. SQHNEBLE, JR. ETAL W METALLIZATION OF INSULATING SUBSTRATES Filed Jan. 5. 1967 15 Sheets-Sheet 2 FREDERICK W. SCHNEBLEJR EDWARD J LEECH JOSEPH POLICHETTE HY MORGAN FINNEGAN, DURHAM 8n PINE ATTORNEYS METALIJIZATION OF INSULATING SUBSTRATES Filed Jan. 5. 1967 15 Sheets-Sheet 5 INVENTORS FREDERICK w SCHNEBLLJR EDWARD J. LEECH JOSEPH POLICHETTE BY MORGAN, FINNEGAMDURHAM 8| PINE ATTORNEYS g 1971 F. w. SCHNEBLE. JR, ETAL 3,609,339

METALLIZATION OF INSULATING SUBSTRATES Filed Jan. 5, 1967 15 Sheets-Sheet 4 INVENTORS FREDERICK W SCHNEBLEJR EDWARD J. LEcH JOSEPH POLICHETTE MORGAN, FINNEGAN, DURHAM 8x PlNE ATTORNEYS 1971 F. w. SCHNEBLE. JR, ETAL 3,600,330

METALLIZATION OF INSULATING SUBSTRATES Filed Jan. 5, 1967 15 Sheets-Sheet 5 INVENTORS 5 k FREDERICK w scrmzmgm EDWARD J. LEECH JOSEPH POLICHETTE FHGTIT MORGAN, FINNEGAN, DURHAM 8: PINE ATTORNEYS Aug. 17, 197E F. w. SCHNEBLE. JR, ETAL 5 9 METALLIZATION OF INSULATING SUBSTRATES Filed Jan. 5, 1967 15 Sheets-Sheet s INVENTOPS. FREDERICK w. SCHNEBLE, m EDWARD J. LEECH JOSEPH POLICHETTE MORGAN, FINNEGAN, DURHAM 8 PINE ATTORNEYS g- 1971 F. w. SCHNEBLE, JR.. ETAL 3,600,330

METALLIZATION OF INSULATING SUBSTRATES Filed Jan. 5, 1967 15 Sheets-Sheet 7 6 FIG?! INVENTORS mensmcx w SCHNEBLE,JR I EDWARD 1.11am

JOSEPH POLICHETTE MORGAN, FINNEGAN, DURHAM 6 PINE ATTORNEYS 1971 F. w. SCHNEBLE, JR, ETAL 3,600,330

METALLIZATION OF INSULATING SUBSTRATES Filed Jan. 5, 1967 15 Sheets-Sheet 8 INVENTORS.

FREDERICK W. SCHNEBLE, JR EDWARD J. LEECH JOSEPH POLICHETTE BY MORGAN, FINNEGAN, DURHAM 8 PINE ATTORNEYS g- 17, 1971 F. w. SCHNEBLE, JR.. ETAL 3,600,330

METALLIZATION OF INSULATING SUBSTRATES Filed Jan. 5. 1967 15 Sheets-Sheet INVENTORS FREDERICK w. SCHNEBLE,JR. EDWARD J. LEECH JOSEPH POLICHETTE BY MORGAN, FINNEGAN, DURHAM 8| PINE ATTORNEYS g- 1971 F. w. SCHNEBLE. JR, ETAL 3.600.330

METALLIZATION 01" INSULATlNG SUUSI'RAI'I'L Filed Jan. 5, 1967 15 Sheets-Sheet 1O INVENTORS FREDERICK w. SCHNEBLE, m.

EDWARD J LEECH JOSEPH POLICHETTE BY MORGAN, FINNEGAN, DURHAM 8| PINE ATTORNEYS Aug. 17, 1971 F. w. SCHNEBLE. JR., ETAL 3,600,330

METALLIZATION OF INSULATING SUBSTRATES Filed Jan. 5, 1967 15 Sheets-Sheet 11 INVENITORS FREDERICK W. SCHNEBLEI JR.

EDWARD J. LEECH JOSEPH POLICHETTE BY MORGAN, FINNEGAN, DURHAM Bu PINE ATTORNEYS Aug- 17, 1971 F. w. SCHNEBLE, JR., ETAIL 3,600,330

METALLIZATION OF INSULATING SUBSTRATES Filed Jan. 5, 1967 15 Sheets-Sheet 12 FIG? 24 INVENTORS (EDWARD J LEECH JOSEPH POLICHETTE MORGAN, FINNEGAMDURHAM 8| PINE ATTORNEYS FREDERICK w. SCHNEBLE,JR.

g 17, 1971 F. w. SCHNILIBLE. JR, ETAL 3,600,330

METALLIZATION OF INSULATING SUBSTRATES Filed Jan. 3, 1967 15 Sheets-Sheet 15 INVENTORS FREDERICK W. SCHINEBLE JR EDWARD J. LEECH JOSEPH POLICHETTE MORGAN, FINNEGAN, DURHAM 8| PINE ATTORNEYS 1971 F. w. SCHNEBLE, JR., ETAL 3,600,330

METALLIZATION OF INSULATING SUBSTRATES Filed Jan. 5, 1967 15 Sheets-Sheet 14 FIG-26 FIG-27 INVENTORS FREDERICK W. SCHNEBLE,JR. EDWARD J. LEECH JOSEPH POLICHETTE MORGAN, FINNEGAN,DURHAM 8| PINE ATTORNEYS g- 1971 F. w. SCHNEBLE, JR, ETAL 3,600,330

METALLIZATION OF INSULATING SUBSTRATES Filed Jan. 5. 1967 15 Sheets-Sheet 15 FIG.'29

INVENTORS FREDERICK w. SCHNEBLE,JR. EDWARD J. LEECH JOSEPH POLICHETTE BY MORGAN, FINNEGAN, DURHAM & PINE ATTORNEYS United States Patent US. Cl. 252-430 9 Claims ABSTRACT OF THE DISCLOSURE There are provided compositions to render insulting substrates catalytic to electroless metal deposition comprising materials, e.g., solid agents, having deposited thereon a cationic wetting agent in combination with an elemental form of a metal from Groups LB and VIII of the Periodic Table of Elements, including mixtures of such metals.

This invention relates to materials and techniques for metalizing insulating substrates generally and for the manufacture of printed circuits particularly.

It is an object of the present invention to provide new and improved insulating blanks which are catalytic to the reception of electroless metal and which can be metallized directly, thereby obviating the necessity for seeding and/or sensitizing.

Another object of this invention is to make rugged and durable metallized objects from such catalytic insulating blanks.

A further object of this invention is to make printed circuit boards from such blanks, including one-layer, twolayer and multi-layer boards.

A further object of this invention is to make from such blanks printed circuit boards, including one-layer, two-layer and multi-layer boards, which are provided with conductive passageways.

An additional object of this invention is to provide materials and techniques for producing high density printed circuit boards, including high density one-layer, two-layer and multi-layer boards which are provided with conductive passageways, or, as more commonly referred to, plated through holes.

Still a further object of this invention is to provide materials and techniques for producing new and improved printed circuit armatures.

Heretofore, in the manufacture of printed circuit boards comprising conductive passageways or holes through insulating panels, it has been customary to seed and sensitize the lateral Walls surrounding the passageways or holes by contacting a perforated substratum sequentially with aqueous acidic solutions of stannous tin ions and precious metal ions, e.g., palladium, or with a single acidic aqueous solution comprising a mixture of stannous tin ions and precious metal ions, such as palladium ions. For example, one such treatment involves immersing the perforated insulating base material first in an aqueous solution of stannous chloride having a pH of about 6.6 to 7.4, followed by washing, after which the substratum is immersed in an acidic aqueous solution of palladium chloride having a pH of about 4.8 to 5.4. In an alternate system, the perforated substratum is simply immersed in a one-step seeder sensitizer acidic aqueous solution comprising a mixture of stannous chloride and palladium chloride.

Such aqueous seeding and sensitizing solutions have important limitations. Hydrophobic plastics cannot be readily wetted with such solutions and therefore the ice sensitization achieved with such materials is ordinarily less than satisfactory. When such aqueous seeding and sensitizing solutions are utilized to sensitize lateral walls of the holes or passageways in panels provided with metal foil on one or more surfaces of the panel, the bond between the hole plating and the surface foil tends to be weak. This is so because use of such seeding and sensitizing systems result in depositing a seeder layer on the surface foil, including the edges thereof which surround the holes. This seeder layer interferes with the bond between the surface foil edges surrounding the holes and electroless metal deposited simultaneously on the edges and on the walls surrounding the holes. It is also frequently necessary to superimpose additional metal on the foil adhered directly to the substratum for a variety of reasons. Thus, the initial foil may not be thick enough for the desired printed circuit component and additional metal may therefore have to be added to thicken the pattern. Alternatively, it is frequently necessary to superimpose on the metal cladding a layer of a different metal in order to impart special characteristics to the circuit. Typically, metals such as nickel, gold, silver and rhodium, including mixtures of such metals, are electroplated or electrolessly deposited on an initial layer of copper foil or cladding during the manufacture of printed circuits from copper clad laminates. When the aqueous seeding and sensitizing solutions of the type described are utilized in the manufacture of such circuits, the bond between the copper and the metal subsequently superimposed on the copper also tends to be weak. Here again, the weakness is attributable to the intermediate seeder layer formed on the metal cladding by the seeder-sensitizer solutions of the type described.

As will be clear from the following description, use of the catalytic blanks and compositions of the present invention eliminates the need for such conventional seeding and/or sensitizing solutions and therefore eliminates the problems concomitant with the use thereof. Very importantly, use of the catalytic blanks and compositions of this invention insures a strong bond between the laminate foil bonded to the catalytic blank and electroless metal deposited on the blank, e.g., on walls surrounding holes, since no intermediate seeder layer is present to interfere with the bond. Also important is the fact that use of these catalytic blanks and compositions leads to the achievement of uniformly high bond strengths between the insulating substratum itself and the electroless metal deposit.

Other objects and advantages of the invention will be set forth in part herein and in part will be obvious herefrom or may be learned by practice with the invention, the same being realized and attained by means of the instrumentalities and combinations pointed out in the appended claims.

The invention consists in the novel parts, constructions, arrangements, combinations and improvements herein shown and described. The accompanying drawings referred to herein and constituting a part hereof, illustrate certain embodiments of the invention and together with the specification serve to explain the principles of the invention.

The compositions of the present invention represent an improvement over the seeding and/ or sensitizing systems heretofore employed. They are extremely easy to prepare, are readily responsive to deposition when exposed to electroless metal baths; are adaptable to a wide variety of substrata and processing conditions; and are also quite economical.

Very importantly, the compositions of this invention utilize relatively small amounts of catalytic metals of 3 Groups LB and VIII of the Periodic Table of Elements and thus permit eflicient utilization of such metals generally, and the precious metals in those groups particularly.

The seeding systems of the present invention are also non-conducting in nature thereby rendering them highly useful for making printed circuits by both positive and negative print techniques.

According to this invention, solid agents which are catalytic to the reception of electroless metal are provided which comprise, in combination, finely divided, inert solid particles having a deposit thereon which comprises a nitrogen or phosphorus containing cationic wetting agent, in combination with one or more metals in elemental form selected from Groups I-B or VIII of the Periodic Table of Elements.

Also according to the present invention, there are provided insulating compositions catalytic to the reception of electroless metal which comprise such agents.

In making the catalytic agents of this invention, the solid particles may be pre-treated with a cationic wetting agent of the type described following which they are treated to deposit thereon a Group I-B or VIII metal. Alternatively, the wetting agent may be incorporated as a component of a medium used to precipitate a Group I-B or VIII metal onto the inert particles. In still another embodiment, the inert particles may be pre-treated with the cationic wetting agent, and then exposed to a medium containing the same or different cationic wetting agent together with an agent or agents capable of precipitating on the solid particles a Group LB or VIII metal which is catalytic to the reception of electroless metal.

Suitable finely divided, inert, insulating solid materials for use in the practice of this invention include fillers, such as aluminum silicate, silica gel, asbestos, albalith, silica, mica, flint powder, quartz, cryolite, calcium sulfate, Portland cement, limestone, atomized alumina, barytes, talc, pyrophyllite, diatomaceous earth, and other like materials. Also may be mentioned pigments, such as titanium dioxide, cadmium red, aluminum powder, and the like. Also may be mentioned such porous materials as paper, wood, Fiberglas, cloth, fibers, such as natural and synthetic fibers, e.g., cotton fibers, polyester fibers, and the like.

The exact size of the inert, finely divided solid materials will depend upon the particular solid and the intended application of the compositions. Typically, such solids will have a minimum dimension which is between about 40 mesh and 600 mesh (U.S. Std. Series).

Preferred for use as the inert, solid material is kaolin clay. Kaolin clay or kaolin is a term used to describe several hydrated aluminosilicate minerals, generally of platelike structure, and comprising as species: kaolinite, nacrite, halloysite and dickite. Kaolinitic minerals are described by the general formula Al O .2SiO .XH O, in which X is usually 2. The weight ratio of SiO to A1 indicated by this formula is 1.18 and kaolin clays normally possess SiO /Al O ratios of from 1.0 to 1.5. Kaolin differs from other clay minerals not only in composition and lattice orientation but also in base-exchange value, the base-exchange value of kaolinitic clays ordinarily ranging from about 3 to 15 milliequivalents per 100 grams.

The cationic surface active agents suitable for use herein are characterized by a hydrophobic group which forms part of the cation when the agent is dissolved in water. Suitable for use are the nitrogen and phosphorus containing cationic surface active agents of the type described in Schwartz & Perry, Surface Active Agents, vol. I, Interscience Publications Inc., 1949, pp. 151-201, which is hereby incorporated herein by reference.

Among the nitrogen containing surfactants may be mentioned quaternary ammonium compounds; sarcosine derivatives; imidazolines; ethoxylated amines and amides; alkanol amides; amines; amides; and cationic surfactants derived from heterocyclic nitrogen COrnpounds, such as pyrrole, pyrrolidone, piperidine, pyridine and the like. Of the phosphorus containing surfactants, preferred for use are the cationic surface active phosphonium'compounds. For best results, the inert solid particles are coated with the cationic wetting agent prior to deposition of the catalytic metal. The coating preferably is accomplished by milling the clay and cationic wetting agent together.

Among the preferred cationics, primary, secondary and tertiary alkyl or aryl-alkyl amines and polyamines with branched and/ or straight chain alkyl groups are all suit able for purposes of the invention. Among this group, primary amines with straight chain alkyl groups are particularly efiicacious. Also particularly suitable for use are those alkyl or aryl-alkyl amines or polyamines containing 4 to 50 carbon atoms in the alkyl chain. As used herein, the term polyamine refers to a compound of the type described which contains two or more amino-nitrogen groups.

Also suitable as the cationic surfactant may be mentioned acid amides or polyamides produced by reacting carboxylic acids with amines of the type described. The carboxylic acids may be saturated or unsaturated, may contain one or more than one carboxyl groups, and will typically contain between about 1 and 17 carbon atoms. As used herein, the term polyamide refers to a compound which contains two or more amido-nitrogen groups. Such compounds may be formed by reacting polyamines With simple carboxvylic acid compounds, or by reacting polycarboxylic acid compounds with mono-amine compounds.

Representative amides are those produced by reacting alkyl or aryl-alkyl amines or polyamines with monoor polycarboxylic acids containing from 1 to 17 carbon atoms. Typical of such amides are the alkyl or aryl-alkyl amine or polyamine salts of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, perargonic acid, capric acid, lauric acid, myristic acid and palmitic and stearic acid. Of the amides, preferred for use in this invention are primary straight chain alkyl amine acetates, i.e., acetamides.

Also suitable for use as the cationic surfactant are certain fatty acid salts of rosin amines. Although the fatty acid salt of an amine derived from any rosin may be used, it is preferable to use the fatty acid salt of a disproportionated rosin amine, such as so-called Rosin Amine D. The preparation of rosin amine from a rosin acid is described in detail in US. Pat. No. 2,491,913, wherein the method for converting the acid to the corresponding nitrile and subsequently reducing the nitrile to an amine is described. The fatty acid salt of rosin amine may be prepared by reacting equal molar quantities of the rosin amine with a fatty acid at a temperature elevated sufliciently to fluidize the fatty acid. Any rosin or modified rosin may be used in the preparation of the rosin amine, suitable rosins including wood rosin, gum rosin or the pure acids, such as abietic or pimaric acids contained therein. Suitable modified rosins include polymerized rosin, heat-treated rosin, isomerized rosin, hydrogenated and dehydrogenated rosin or the pure acids derived therefrom such as dihydroabietic and tetrahydroabietic acids. Hydroabietylamine is ultimately derived from the dehydrogenation of natural rosin With an active hydrogenation catalyst in the absence of hydrogen. The natural rosin, hydrogenated, dehydrogenated or other modified rosin may be refined by any appropriate means means well-known to those skilled in the art prior to conversion to the amine.

Among the carboxylic acids that may be reacted with the rosin amines may be mentioned alkanoic acids containing 1 to 17 carbon atoms in the alkyl chain. Preferred for use are stearic acid and myristic acid.

Also suitable for use as the cationic Wetting agent are derivatives of sarcosine produced by reacting sarcosine (methylaminoacetic acid) with any fatty acid of the type described above. Stearic, palmitic and oleic are preferred.

Such sarcosine derivatives may be considered as modified fatty acids in which the hydrocarbon chain is interrupted The catalytic metal of Groups IB and VIII of the Periodic Table of Elements may be deposited on the filler material in variety of ways. For example, such metals could be vapor deposited on the finely divided inert solids. Alternatively and preferably, a slurry of a soluble salt of a catalytic metal, a suitable reducing agent and the iner solid material is prepared, such that the salt of the catalytic metal is reduced to deposit or precipitate catalytic metal directly on the inert solid material.

The catalytic metal deposited on the inert solids may be any metal of Groups I-B and VIII of the Periodic Table but is preferably nickel, gold, silver, platinum, palladium, rhodium, copper or iridium. Compounds of such metals, including water soluble salts, e.g., nitrates, chlorides, sulfates, etc., and oxides thereof, will be used in producing solutions from which the catalytic metal is precipitated.

In making the catalytic compositions, a variety of techniques may be utilized. Thus, the catalytic particles could be dispersed in an organic resin and the resulting resin used to impregnate laminates, such as paper, wood, Fiberglas, polyester fibers and other porous laminates. These base materials, for example, could be immersed in a resin containing the catalytic solids or a resin containing the catalytic solids could be sprayed onto the base material, after which the base materials could be dried in an oven until all the solvent has evaporated leaving a laminate of the type described impregnated with the catalytic particles. If desired, the laminates could be bonded together to form a base of any desired thickness.

Alternatively, the catalytic solids could be dispersed in a resinous material, which in turn could be molded into a base of the desired size, as by molding.

A further alternative would be to preform or premold thin films or strips of unpolymerized resin having dispersed therein the catalytic solids, and then laminate a plurality of the strips together to form a catalytic insulating base of the desired thickness. In any event, it will be appreciated that the interior of the insulating base will be catalytic throughout, such that, when holes or apertures are formed therein at any part, the walls of the holes or apertures will be sensitive to the receptionof electroless metal from an electroless metal chemical deposition solution such as an electroless copper solution.

The surface of the insulating catalytic base may or may not be catalytic, depending upon how it is made, concentration of catalytic filler, and the like. The surface could be made catalytic by mechanical means, as by mild abrasion, e.g., by sand blasting, or by chemical means, as by treatment with chemical solvents, etchants, milling solutions, and the like. A preferred chemical treatment for rendering the surface catalytic is to treat the surface with acids, preferably oxidizing acids, e.g., sulfuric, nitric, chromic and the like. Alternatively, the exposed surface or surfaces of the catalytic bases could be made catalytic by coating them with a thin film of an adhesive or ink having dispersed therein the catalytic fillers described herein.

Catalytic solids of the type described could also be incorporated into a resin during its manufacture in the form, for example, of a molding powder. The molding powder could then be extruded or otherwise Worked to form a plastic article which would be catalytic.

The catalytic insulating base need not be organic. Thus, it could be made of inorganic insulating materials, e.g., inorganic clays and minerals such as ceramic, ferrite, carborundum, glass, glass bonded mica, steatite and the like. Here, the catalytic agent would be added to inorganic clays or minerals prior to firing.

The term catalytic as used herein refers to an agent or material which is catalytic to the reduction of the metal cations dissolved in electroless metal deposition solutions of the type to be described. The amount of catalytic agent used in the bases and adhesive resins described will vary depending upon the agent and the form in which it is used from about 0.0005 to 8051, usually between about 0.1 to 10%, based upon thee omtbined weight of base material or adhesive resin and catalyst.

Among the organic materials which may be used to form the catalytic insulating bases and adhesives described herein may be mentioned thermosetting resins, thermoplastic resins and mixtures of the foregoing.

Among the thermoplastic resins may be mentioned the acetal resins; acrylics, such as methyl acrylate; cellulosic resins, such as ethyl cellulose, cellulose acetate, cellulose propionate, cellulose acetate butyrate, cellulose, nitrate, and the like; chlorinated polyethers; nylon; polyethylene; polypropylene; polystyrene; styrene blends, such as acrylonitrile styrene co-polymer and acrylonitrile-butadiene-styrene co-polymers; polycarbonates; polychlorotrifiuoroethylene; and vinyl polymers and co-polymers, such as vinyl acetate, vinyl alcohol, vinyl butyral, vinyl chloride, vinyl chloride-acetate co-polymer, vinylidene chloride and vinyl formal.

Among the thermosetting resins may be mentioned allyl phthalate; furane; melamine-formaldehyde; phenol formaldehyde and phenol-furfural co-polymer, alone or compounded with butadiene acrylonitrile co-polymer or acrylonitrile-butadiene-styrene co-polymers; polyacrylic esters; silicones; urea formaldehydes; epoxy resins; allyl resins; glyceryl phthalates; polyesters; and the like.

For the manufacture of printed circuits, the catalytic adhesive will ordinarily comprise a flexible adhesive resin, alone or in combination with thermosetting resins of the type described. Typical of the flexible adhesive resins which may be used in such a system are the flexible adhesive epoxy resins, polyvinyl acetal resins, polyvinyl alcohol, polyvinyl acetate, and the like. Preferred for use as the adhesive resin are natural and synthetic rubber, such as chlorinated rubber, butadiene acrylonitrile co-polymers, and acrylic polymers and co-polymers.

The adhesive resins of the type described have appended thereto polar groups, such as nitrile, epoxide, acetal and hydroxyl groups. Such adhesive resins co-polymerize with and plasticize any thermosetting resins which may be present in the system, and alone or in combination with thermosetting resins impart good adhesive characteristics through the action of the polar groups.

The catalytic adhesives will comprise an adhesive resin of the type described having dispersed therein the catalytic agents described herein.

When present in an adhesive resin of the type described, regardless of the manner in which it is incorporated, the active catalytic agent, depending upon type, will be present in amounts varying from a small fraction, e.g., 0.0005% to about preferably 0.5 to 10%, based upon the combined weight of adhesive resinous material and catalyst. The particular concentrations used will depend to a large extent upon the materials used.

Typical formulations for catalytic insulating adhesives or inks and catalytic insulating bases suitable for use herein are given in co-pending application Ser. No. 218,656, which is in turn a continuation-inpart of US. Pat. 3,226,- 256, and also in Ser. No. 390,624, the disclosures of which applications and patents are herein incorporated by reference.

Typically, the autocatalytic or electroless metal deposition solutions for use with the catalytic insulating bases and adhesives described comprise an aqueous solution of a water soluble salt of the metal or metals to be deposited, a reducing agent for the metal cations, and a complexing or sequestering agent for the metal cations. The function of the complexing or sequestering agent is to form a water soluble complex with the dissolved metallic cations so as to maintain the metal in solution. The function of the reducing agent is to reduce the metal cation to metal at the appropriate time, as will be made more clear hereinbelow.

Typical of such solutions are electroless copper, electroless nickel and electroless gold solutions. Such solutions are well known in the art and are capable of autocatalytically depositing the identified metals without the use of electricity.

Typical of the electroless copper solutions which may be used are those' described in Us. Pat. 3,095,309, the description of which is incorporated herein by reference. Conventionally, such solutions comprise a source of cupric ions, e.g., copper sulfate, a reducing agent for cupric ions, e.g., formaldehyde, a complexing agent for cupric ions, e.g., tetrasodium ethylenediaminetetraacetic acid, and a pH adjustor, e.g., sodium hydroxide.

Typical electroless nickel baths which may be used are described in Brenner, Metal Finishing, November 1954, pages 68 to 76, incorporated herein by reference. They comprise aqueous solutions of a nickel salt, such as nickel chloride; an active chemical reducing agent for the nickel salt, such as the hypophosphite ion; and a complexing agent, such as carboxylic acids and salts thereof.

Electroless gold plating baths which may be used are disclosed in US. 2,976,181, hereby incorporated herein by reference, They contain a slightly water soluble gold salt, such as gold cyanide, a reducing agent for the gold salt, such as the hypophosphite ion, and a chelating or complexing agent, such as sodium or potassium cyanide. The hypophosphite ion may be introduced in the form of the acid or salts thereof, such as the sodium calcium and the ammonium salts. The purpose of the complexing agent is to maintain a relatively small portion of the gold in solution as a water soluble gold complex, permitting a relatively large portion of the gold to remain out of solution as a gold reserve. The pH of the bath will be about 13.5, or between about 13 and 14, and the ion ratio of hypophosphite radical to insoluble gold salt may be between about 0.33 and 10: 1.

Specific examples of electroless copper depositing baths suitable for use will now be described:

EXAMPLE 1 Moles/liter Copper sulfate 0.03 Sodium hydroxide 0.125 Sodium cyanide 0.0004 Formaldehyde 0.08 Tetrasodium ethylenediaminetetraacetate 0.036 Water Remainder This bath is preferably operated at a temperature of about 55 C, and will deposit a coating of ductile electroless copper about 1 mil. thick in about 51 hours.

Other examples of suitable baths are as follows:

EXAMPLE 2 Moles/liter Copper sulfate 0.02 Sodium hydroxide 0.05 Sodium cy-anide 0.002

Trisodium N hydroxyethylethylene diaminetriacetate 0.032 Formaldehyde 0.08 Water Remainder This bath is preferably operated at a temperature of about 56 C. and will deposit a coating of ductile electroless copper about 1 mil. thick in 21 hours.

EXAMPLE 3 Moles/liter Copper sulfate 0.05 Diethylenetriamine pentaacetate 0.05 Sodium borohydride 0.009

Sodium cyanide 0.008 pH, 13. Temperature 25 C.

EXAMPLE 4 Moles/liter Copper sulfate 0.05 N-hydroxyethylethylenediaminetriacetate 0.1 15 Sodium cyanide 0.0016 Sodium borohydride 0.008 pH, 13.

Temperature 25 C.

Utilizing the electroless metal baths of the type described, very thin conducting metal films may be laid down. Ordinarily, the metal films superimposed by electroless metal deposition will range from 0.1 to 7 mils. in thickness, with metal films having a thickness of even less than 0.1 mil being a distinct possibility.

The following examples illustrate the manner in which the catalytically active solid particles of this invention may be produced.

EXAMPLE 5 This example illustrates the technique for treating kaolin with a cationic wetting agent. A solution of a cationic wetting agent was prepared as follows:

Sarkosyl O (oleyol sarcosine)20 grams Isopropanol ml.

One hundred grams of water-washed kaolin clay purchased under the trade name ASP 400 was mixed with the solution for several minutes. The kaolin was then filtered from the solution and dried at C. for 1 hour.

EXAMPLE 6 One hundred and sixty grams of stannous chloride was dissolved in one hundred (100) milliliters of hydrochloric acid. To this solution was added, while stirring, two (2) grams of palladium chloride in 40 milliliters of hydrochloridic acid. The solution was boiled for 30 minutes. After cooling, it was diluted to 1 liter with 0.1 molar aqueous hydrochloric acid. 50 grams of the Sarkosyl 0 treated kaolin of Example 5 was mixed with 100 milliliters of this solution. All the palladium was removed from the solution by the kaolin, which after drying was suitable for use as a catalytic filler.

EXAMPLE 7 Cationic wetting agent treated kaolin clay prepared substantially as described in Example 5 was treated with gold chloride to produce a gold catalyst by mixing 0.94 gram of gold chloride, 100 ml. of water and 50 grams of the treated kaolin. To the admixture was then slowly added 2% stannous chloride solution until all the gold was deposited from the solution onto the filler (50 milliliters of the 2% stannous chloride was sufiicient). A casting was prepared containing 1 part gold treated filler in 3 parts untreated filler and 8 parts of a polyester resin. Electroless copper readily deposited on the walls of holes drilled in this casting when the casting was exposed to an electroless copper solution of the type described hereinabove. 8

EXAMPLE 8 A cationic wetting agent treated clay prepared substantially as described in Example 5 was treated with silver nitrate to produce a silver catalyst base material by dissolving 21.2 grams silver nitrate in 1 liter of water and then adding 500 grams of the treated filler. The resulting slurry was treated with 750 ml. of a 40 grams/liter stannous chloride aqueous solution to deposit the silver on the filler; and then filtered, washed Well and dried. When this filler was incorporated into a polyester casting, the resultant casting was found to be readily catalytic to the deposition of electroless copper from electroless copper solutions of the type described herein.

EXAMPLE 9 I Kaolin clay coated with lRosin (Amine D was treated to produce a palladium catalyzed base material. In 1 liter of water was dissolved 6 milliliters of concentrated hydrochloric acid. Five hundred and forty (540) grams of the Rosin Amine D coated kaolin clay was added to the solution and mixed for 30 minutes. Then there was added a palladium chloride solution (1.07 grams of palladium chloride dissolved in 1.2 milliliters of hydrochloric acid and diluted to a total volume of 30 milliliters with water). This was thoroughly mixed with the filler slurry and then, with constant stirring, a solution of stannous chloride was added (this solution was prepared by dissolving 10.7 grams of SnCl .2H O in 60 milliliters of water and then adding hydrochloric acid until the solution was clear). After thoroughly mixing, the slurry was filtered, and the filler was washed and dried at l05-l20 C. After drying, the palladium treated filler was ground to break up agglomerates and then incorporated into a paper base phenolic laminate. Six (6) parts treated filler per 100 parts resin was used. Electroless copper readily deposited on the walls of holes drilled in this laminate without any pre-sensitizing treatment of the laminate.

EXAMPLE 10 A palladium solution was prepared as follows:

Eight hundred (800) grams of stannous chloride was dissolved in half a liter of hydrochloric acid. To this tin solution was slowly added, with stirring, a solution of 10 grams of palladium chloride in 200 milliliters hydrochloric acid. The solution was then brought to a gentle boil for at least /2 hour. After cooling it was diluted to 5 liters with 0.1 molar aqueous hydrochloric acid solution.

Five (5) kilograms of kaolin coated with Rosin Amine D cationic wetting agent was stirred into the dilute solution and mixed for /2 hour. The filler was then filtered out, washed thoroughly and dried. Six and one-half (6 /2) parts of the resulting filler per 100 parts of resin were incorporated into an epoxy glass laminate. The laminate was exposed to an electroless copper solution of the type described herein and readily received a deposit of electroless copper on the walls of holes punched in the laminate.

EXAMPLE 11 Nine (9) kilograms of stannous chloride was dissolved in 85 liters of water and 2 /2 liters of hydrochloric acid. One hundred (100) pounds of kaolin coated with Rosin Amine D cationic wetting agent was stirred into this solution. Next, there was added 2 /2 liters of an aqueous solution containing 91 grams palladium chloride and 110 milliliters hydrochloric acid. After thorough mixing, the slurry was filtered and the filler washed, dried and incorporated into a polyester glass laminate on a basis of 6 parts filler per 100 parts resin. Holes were drilled in the resulting sheet and the sheet immersed in an electroless copper solution substantially of the type described herein. The walls surrounding the holes readily received a deposit of electroless copper.

As described above, in another method of treating a filler to make it catalytic, the catalytic agent is first dissolved in a cationic wetting agent and the resulting medium used to treat the filler. A typical procedure is as follows:

EXAMPLE 12 Four tenths (0.4) of a milliliter of a solution of palladium chloride in hydrochloric acid containing 0.85 gram palladium chloride per milliliter is dissolved in 250 milliliters of isopropyl alcohol and 3 milliliters of Sarkosyl O (oleoyl sarcosine). One hundred and twenty-five (125) grams of water washed kaolin was dispersed in this solution and /2 liter of water was added. The kaolin was filtered from the solution and dried. Resin castings were made from the following formulation:

Polyester resin (Laminac 4128)40 grams Treated catalytic filler-5 grams Kaolin (ASP 400)-l5 grams Benzoyl peroxide-0.6 gram Promoter (Laminac 400)-1 drop Castings corresponding to the formulation given above were made using the resulting catalytic fillers. Holes were drilled in the castings, following which they were immersed in an electroless copper plating solution containing the following formulation:

Copper sulfate0.06 mole/liter EDTA0.12 mole/liter Formaldehyde-0.08 mole/liter Sodium cyanide-0.6 millimole/ liter Wetting agent1.0 gram/liter Z-mercaptobenzothiazole0.003 millimole/liter pH-l 1.8

Operating temperature68 C.

The casting received an electroless copper deposit on the walls of the hole in 30 minutes.

EXAMPLE l3 Palladium solutions were prepared as follows:

Grams Palladium chloride in 50 ml. of octyl amine acetate 0.5 Palladium chloride in 50 ml. of hexylamine acetate 0.5 Palladium chloride in 50 ml. of butyl amine acetate" 0.5 Palladium chloride in 50 ml. of Amine O 1 0.5 Palladium chloride in 50 ml. of Sarcosyl O (oleoyl) sarcosine) 0.5

1 Amino O is a cationic weuting agent of the general formula CI'IQICHflnCIZZ N[CH3}2 1TIR The resulting solutions were added to resin laminates in amounts sufficient to render the laminates catalytic to the reception of electroless metal. As a comparison, a laminate was prepared as described in Example 11, utilizing the surfactant treated catalytic filler. It was dis covered that in order for the laminates to which the solutions were added to exhibit acceptable catalytic activity, 10 to times more palladium (as the chloride) was required than was required to catalyze the same base using the cationic surfactant treated catalytic fillers of Example 11.

The catalytic agents described herein may be used in a variety of ways as already brought out. For example, they could be conveniently used as fillers in resins used to impregnate paper, wood, Fiberglas cloth and the like to produce structures which are catalytic to the reception of electroless metal.

The catalytic agents could also be incorporated into a suitable composition to be used as an ink to paint surface areas on which electroless metal is to be deposited.

The insulating base members on which electroless metal is to be deposited are most frequently formed of resinous material. When this is the case, the catalytic agents disclosed herein could be dispersed into a resin after which the resin could be set to form the base. Alternatively, a thin film or strip of unpolymerized resin having dispersed therein the catalytic solids of this invention could be preformed or premolded, and then laminated to a resinous insulating base, and cured thereon. In this embodiment, the insulating base could for example be made up of laminates, e.g., resin impregnated paper sheets, resin impregnated Fiberglas sheets, and the like.

In still a further embodiment, a resinous ink having the catalytic agent dispersed therein could be printed on the surface, as by silk screen printing, of an insulating support and cured thereon.

A particularly important embodiment of the invention is that wherein the catalytically active solids are dispersed in a resin which may in turn be formed into a threedimensional object, as by molding. In this embodiment, the entire composition including the interior is catalytic. When such an article, containing apertures extending below the surface thereof, is subjected to an electroless metal deposition solution, electroless metal deposits not only on the exposed portions of the surface of the article, but also on the walls surrounding the apertures. This 

